Xylylene diisocyanate composition and method for producing same

Abstract

The present invention relates to a technology relating to a xylylene diisocyanate composition in which the content of low-boiling point compounds is controlled, and a method for producing the same, and the technology relates to a xylylene diisocyanate composition and a method for producing the same, which can produce a high-purity xylylene diisocyanate compound in high yield by controlling the purity of an amine compound and adjusting the content range of low-boiling point compounds in the reaction product during the production of xylylene diisocyanate using phosgene.

Description

[Technical Field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims the benefit of priority based on Korean Patent Application No. 10-2022-0153715, filed November 16, 2022, and Korean Patent Application No. 10-2023-0159228, filed November 16, 2023, and all contents disclosed in the documents of said Korean patent applications are incorporated herein by reference.

[0002] The present invention relates to a process for producing a cellulose ester having a low boiling point compound content controlled. Xylylene diisocyanate The present invention relates to a composition and a method for producing the same. [Background technology]

[0003] Xylylene diisocyanate Although xylylene diisocyanate (hereinafter referred to as XDI) contains an aromatic ring, it is classified as an aliphatic isocyanate and is a very useful compound as a raw material for polyurethane-based materials, polyurea-based materials, polyisocyanurate-based materials, etc. in the chemical, resin, and paint industries.

[0004] Aliphatic isocyanates are usually produced by a phosgenation method in which a raw material amine is reacted with phosgene. For example, in the case of XDI, Xylylenediamine It is produced by reacting xylylene diamine (XDA) with phosgene. However, XDI has similar properties to aliphatic isocyanates, and the amino group is highly reactive, which causes many side reactions during the phosgenation reaction. The impurities formed by these side reactions affect the reaction that forms the polyurethane resin, resulting in a deterioration in the quality of the resin.

[0005] In response to this, various methods have been researched and proposed to reduce the content of generated impurities and produce high-purity XDI.

[0006] Specifically, Korean Patent Publication No. 1994-0001948 states: Xylylenediamine or by the reaction of its hydrochloride with phosgene Xylylene diisocyanate However, this method has problems such as high solvent cost, low purity, and low yield.

[0007] Korean Patent Registration No. 0953019 discloses a method of applying pressure during a salt formation process in which an amine hydrochloride is prepared by reacting a linear or cyclic aliphatic amine with hydrogen chloride, and then an isocyanate is formed by a phosgene reaction to solve the problem of transporting the amine hydrochloride.

[0008] As a non-phosgenation method that does not use phosgene, Korean Patent Registration No. 1318828 describes a non-phosgene method in which a diamine compound is reacted with an alkyl chloroformate or a dialkyl carbonate to produce a biscarbamate, which is then thermally decomposed to decompose and remove an alcohol with a relatively low boiling point. Xylylene diisocyanate However, this method is disadvantageous in terms of cost compared to the phosgene method, and is difficult to apply to industrial mass production. Summary of the Invention [Problem to be solved by the invention]

[0009] The present invention relates to a process for producing a cellulose ester having a low boiling point compound content controlled. Xylylene diisocyanate This technology relates to a composition and a method for producing the same.

[0010] The present invention uses phosgene Xylylene diisocyanate During the production of amine compounds, the purity of the amine compounds is controlled and the content range of specific low boiling point compounds in the reactants is adjusted to produce high purity amine compounds. Xylylene diisocyanate Compounds can be produced in high yields Xylylene diisocyanate The present invention provides a method for producing the above compound.

[0011] In addition, the present invention increases the process efficiency of the phosgene reaction by performing the salt formation reaction under specific conditions and utilizing the reaction heat generated in the reaction, thereby producing high-purity phosgene. Xylylene diisocyanate A method for producing a compound economically is provided. [Means for solving the problem]

[0012] According to one embodiment of the present invention, Xylylene diisocyanate compounds; and low-boiling compounds including isocyanomethylbenzaldehyde and isocyanomethylbenznitrile; The low-boiling point compound is contained in an amount of 1% or less of the total content of the composition. Xylylene diisocyanate A composition is provided.

[0013] According to one embodiment of the invention, The first step is to react an amine compound with hydrogen chloride in a solvent at 20°C to 90°C and atmospheric pressure to obtain an amine salt compound; Amine salt compounds are reacted with phosgene to form Xylylene diisocyanate A second step of obtaining a reaction mixture containing the compound; and removing the solvent and unreacted phosgene from the reaction mixture; Xylylene diisocyanate a third step of producing the composition, the solvent is at least one selected from the group consisting of chlorobenzene, 1,2-dichlorobenzene, 1,4-dichlorobenzene, 1,2,3-trichlorobenzene, and 1,2,4-trichlorobenzene; The purity of the amine compound is 99.0% or more, The aforementioned Xylylene diisocyanate The composition contains 1% or less of low-boiling compounds based on the total content of the composition, and the low-boiling compounds include isocyanomethylbenzaldehyde and isocyanomethylbenznitrile. Xylylene diisocyanate A method for making the composition is provided.

[0014] According to another embodiment of the invention, The first step is to react an amine compound with hydrogen chloride in a solvent at 20°C to 90°C and atmospheric pressure to obtain an amine salt compound; Amine salt compounds are reacted with phosgene to form Xylylene diisocyanatea second step of obtaining a reaction mixture containing the compound; removing the solvent and unreacted phosgene from the reaction mixture; Xylylene diisocyanate A third step of preparing the composition; and The aforementioned Xylylene diisocyanate a fourth step of polymerizing the composition and the polyhydric alcohol to synthesize a polyisocyanate compound; the solvent is at least one selected from the group consisting of chlorobenzene, 1,2-dichlorobenzene, 1,4-dichlorobenzene, 1,2,3-trichlorobenzene, and 1,2,4-trichlorobenzene; The purity of the amine compound is 99.0% or more, The aforementioned Xylylene diisocyanate A method for producing a polyisocyanate composition is provided, wherein the composition contains 1% or less of a low-boiling compound based on the total content of the composition, and the low-boiling compound includes isocyanomethylbenzaldehyde and isocyanomethylbenznitrile.

[0015] According to another embodiment of the invention, As mentioned above Xylylene diisocyanate composition; and A polymerizable composition is provided that includes one or more of i) a multifunctional thiol-based compound and ii) a multifunctional episulfide-based compound.

[0016] According to another embodiment of the invention, Optical articles are provided that include polythiourethane polymers made from the polymerizable compositions. [Effects of the Invention]

[0017] According to the present invention Xylylene diisocyanate The content range of the specific low-boiling point compound in the composition is controlled, and a high-purity polyisocyanate compound can be produced in high yield without generating additional impurities during polyisocyanate synthesis.

[0018] Also, the present invention Xylylene diisocyanateThe method for producing the composition is a simple process for adjusting the purity of the reaction composition and simultaneously adjusting the content range of specific low-boiling compounds in the by-products, thereby producing a high-purity Xylylene diisocyanate The compound can be produced in high yield. Xylylene diisocyanate The method for producing the composition involves adjusting the conditions for the amine compound salt formation reaction within an appropriate range, thereby increasing the process efficiency in the subsequent phosgene reaction and producing a high-purity product. Xylylene diisocyanate The compounds can be produced economically.

[0019] Furthermore, the method for producing a polyisocyanate composition according to the present invention can produce a high-purity polyisocyanate compound in high yield by adjusting the purity of the reaction composition and simultaneously adjusting the content range of a specific low-boiling point compound in the by-product. DETAILED DESCRIPTION OF THE INVENTION

[0020] The terms used in this specification are merely used to describe exemplary embodiments and are not intended to limit the present invention. The singular expressions include the plural expressions unless the context clearly indicates otherwise. It should be understood that the terms "comprise," "comprise," or "have" used in this specification are intended to specify the presence of embodied features, numbers, steps, components, or combinations thereof, and do not preclude the possibility of the presence or addition of one or more other features, numbers, steps, components, or combinations thereof.

[0021] Although the present invention can be embodied in various forms through various modifications, specific embodiments are described in detail below by way of example, but it should be understood that this is not intended to limit the present invention to the specific disclosed embodiments, and that the present invention encompasses all modifications, equivalents, and alternatives falling within the spirit and technical scope of the present invention.

[0022] Typically, the production of an isocyanate compound using a phosgenation reaction is carried out by reacting an amine compound with phosgene, which generates various impurities as by-products. The present inventors have investigated the effects of applying a polyisocyanate polymerized using an isocyanate containing such various impurities to an actual product, and have confirmed that a high-purity isocyanate can be produced in high yield by controlling the purity of the reactants, the solvent and the amine compound, and simultaneously controlling the content of low-boiling-point compounds in the reaction mixture within a specific range (about 1% or less), thereby completing the present invention.

[0023] In particular, low-boiling point compounds in the reaction by-products can generate additional impurities during polyisocyanate synthesis, inhibiting catalyst activity and affecting the reaction rate, thereby affecting product quality. However, by adjusting the content within the appropriate range as described above, it is possible to produce high-quality products without these problems, and such high-purity polyisocyanate compounds can significantly reduce the reject rate and improve reproducibility when applied to optical articles.

[0024] Furthermore, the amine compound used in the phosgene reaction is produced in the form of a chloride by a salt formation reaction. In the present invention, the salt formation reaction is carried out in a specific solvent under relatively mild conditions, so that the phosgene reaction can be easily carried out without additional cooling or heating steps, resulting in excellent economy.

[0025] < Xylylene diisocyanate Composition> According to one embodiment of the invention, Xylylene diisocyanate and low-boiling compounds including isocyanomethylbenzaldehyde and isocyanomethylbenznitrile; wherein the low-boiling compounds are contained in an amount of 1% or less based on the total content of the composition. Xylylene diisocyanateThe range of the content of the low-boiling point compound is a GC area (%) measured by gas chromatography (GC), and the specific measurement method will be described in more detail in the experimental examples below.

[0026] On the other hand, if the low boiling point compound is contained in the composition in an amount exceeding 1%, additional impurities may be generated during the synthesis of polyisocyanate, which may inhibit the activity of the catalyst and affect the reaction rate. This may affect the quality of the product, but when the content is adjusted to the appropriate range as described above, Xylylene diisocyanate Use of the composition makes it possible to produce a high-purity polyisocyanate without such problems, and such a polyisocyanate compound can significantly reduce the reject rate when applied to optical articles and improve reproducibility.

[0027] The content of the low boiling point compound is preferably Xylylene diisocyanate The content of the low-boiling point compound may be 0.7% or less, 0.5% or less, or 0.3% or less relative to the total content of the composition. The lower limit of the content of the low-boiling point compound is 0% or more, preferably 0.0001% or more, 0.0001% to 0.7%, or 0.001 to 0.5%, and the content range is suitable for achieving the above-mentioned effects.

[0028] The isocyanomethylbenzaldehyde (IMBAl) may be contained in an amount of 0.0001 to 0.15%, preferably 0.001 to 0.15%, or 0.0003 to 0.11%, relative to the total content of the composition.

[0029] The isocyanomethylbenznitrile (IMBN) may be contained in an amount of 0.0001 to 0.1%, preferably 0.0003 to 0.1%, or 0.0008 to 0.06%, relative to the total content of the composition.

[0030] According to one embodiment of the present invention, the low-boiling point compound may further include chloromethyl benzyl isocyanate (CMBI), in which case the chloromethyl benzyl isocyanate may be contained in an amount of 0.01 to 0.2%, preferably 0.05 to 0.15%, based on the total content of the composition.

[0031] The aforementioned Xylylene diisocyanate In addition to the above components, the composition may further contain additional additives to maintain storage stability.

[0032] The type of the additional additive is not particularly limited, and may further include antioxidants, heat stabilizers, polymerization inhibitors, etc. that are commonly used in the art. The content of the additive is not particularly limited, and can be used in an appropriate range as long as the object of the present invention is not impaired.

[0033] The aforementioned Xylylene diisocyanate The composition has excellent physical properties and can be used in a wide range of fields, particularly in optical articles.

[0034] The aforementioned Xylylene diisocyanate The composition can be produced by the production method described below.

[0035] < Xylylene diisocyanate Method for producing the composition> Specifically, according to one embodiment of the invention: Xylylene diisocyanate The method for producing the composition includes the steps of: reacting an amine compound with hydrogen chloride in a solvent at 20°C to 90°C and atmospheric pressure to obtain an amine salt compound; and reacting the amine salt compound with phosgene. Xylylene diisocyanate obtaining a reaction mixture containing the compound; and removing the solvent and unreacted phosgene from the reaction mixture. Xylylene diisocyanate The third step involves preparing the composition.

[0036] (Salt formation reaction) First, an amine compound is reacted with hydrogen chloride in a solvent at 20° C. to 90° C. under normal pressure to obtain an amine salt compound in the first stage (salt formation reaction).

[0037] The salt-forming reaction to obtain the amine salt compound is carried out in a specific solvent at 20°C to 90°C under normal pressure, so that the subsequent phosgene reaction can be easily carried out without additional cooling or heating steps, which is economical.

[0038] Here, atmospheric pressure refers to the pressure without the use of a separate pressure reducing device such as a vacuum pump. For example, atmospheric pressure corresponds to approximately 760 mmHg, which is the general atmospheric condition. This range is preferred because it maintains a uniform phase of the amine salt compound. If the salt formation reaction is carried out under pressure exceeding atmospheric pressure, the particle size of the amine salt compound may become non-uniform.

[0039] On the other hand, if the salt formation reaction is carried out at a temperature below 20°C, the particle size of the amine salt compound may become non-uniform, which may inhibit the subsequent phosgene reaction. Furthermore, if the reaction is carried out at a temperature above 90°C, it becomes difficult to control the salt formation reaction itself. Preferably, the salt formation reaction may be carried out at a temperature between 30°C and 80°C. On the other hand, the temperature of the salt formation reaction can be controlled by the reaction heat generated by adding hydrogen chloride, without the need for special temperature control.

[0040] The solvent is at least one selected from the group consisting of chlorobenzene, 1,2-dichlorobenzene, 1,4-dichlorobenzene, 1,2,3-trichlorobenzene, and 1,2,4-trichlorobenzene. These are inert organic solvents that can reduce the amount of by-products. Furthermore, these solvents have high polarity, which helps dissolve the amine salt compound and facilitates the reaction. 1,2-dichlorobenzene is most preferred. On the other hand, using a solvent such as n-amyl acetate can result in uneven particle size of the amine salt compound, which can inhibit the phosgene reaction.

[0041] Preferably, the purity of the solvent is 99.0% or more, thereby minimizing side reactions in the phosgenation reaction, and in particular, the content of low boiling point compounds in the side reaction products is controlled within the above range to obtain a high purity solvent. Xylylene diisocyanateMore preferably, the purity of the solvent is 99.0% to 99.99%. The above content range is preferable for realizing the above-mentioned effects.

[0042] The purity of the amine compound is 99.0% or more, so that the side reaction in the phosgenation reaction can be minimized. In particular, the content of low boiling point compounds in the side reaction products can be controlled within the above range to obtain a high purity amine compound. Xylylene diisocyanate The amine compound can be produced. Preferably, the purity of the amine compound is 99.0% to 99.99%. The above-mentioned content range is preferable for realizing the above-mentioned effects.

[0043] The amine compound is m- Xylylenediamine , p- Xylylenediamine , o- Xylylenediamine and chlorides thereof (for example, hydrochlorides or carbonates). Preferably, chlorides of the amine compounds can be used. In this case, the chlorides of the amine compounds can be used. Xylylene diisocyanate This is preferable because it can increase the conversion rate to the product and reduce the content of impurities during the production of the compound.

[0044] More specifically, the amine compound can be obtained by the following reaction and exhibit a purity within the aforementioned range: [ka]

[0045] XDA is synthesized by ammoxidizing m-xylene to produce IPN (isophalonitrile) in the first step, followed by a hydrogenation reaction in the second step. Impurities that can be produced in the two-step synthesis process are indicated as #1 to #3, and although various other impurities can also be produced, the amount of impurities is small (less than about 1%).

[0046] On the other hand, the impurities are Xylylene diisocyanateThe process of obtaining a reaction mixture containing the compound may affect the content of low boiling point compounds, that is, the higher the purity of the amine compound, the more the content of low boiling point compounds can be reduced.

[0047] The amine compound may be contained in an amount of 1 to 20% by weight based on the total content of the solvent. If the amine compound content exceeds 20% by weight, the stirring process during the reaction may be difficult, a large amount of the amine compound may precipitate, and the reaction may become non-uniform, which may affect the increase in the content of low-boiling compounds. Preferably, the amine compound may be contained in an amount of 1 to 15% by weight or 5 to 15% by weight.

[0048] (Phosgene reaction) The amine salt compound is then reacted with phosgene to form a Xylylene diisocyanate A second step involves obtaining a reaction mixture containing the compound.

[0049] By carrying out the salt formation reaction under the above-mentioned conditions, a homogeneous chloride phase can be obtained, and the phosgene reaction can be carried out more easily.

[0050] The reaction temperature is not particularly limited, and may be 110° C. to 160° C., more preferably 120° C. to 140° C. If the reaction temperature exceeds 160° C., the concentration of by-products increases, which may cause problems such as thermal decomposition of the reactants and products.

[0051] Preferably, the reaction may be carried out by gradually increasing the temperature inside the reactor so that the temperature falls within the above-mentioned range, and then adding phosgene, or more preferably, by adjusting the temperature inside the reactor to 110°C to 140°C after adding phosgene. The reaction may be carried out by adjusting the temperature of the reactor to 120°C to 135°C.

[0052] According to one embodiment of the present invention, the method of adding phosgene in the reaction between the amine salt compound and phosgene is not particularly limited. For example, the amine salt compound and phosgene may be added to a single reactor and simply stirred, or the reaction may be carried out by injecting phosgene into the reactor containing the amine salt compound through a mixing eductor, which is a mixing nozzle. Preferably, the phosgene may be injected through a mixing eductor in order to uniformly mix the reactants and improve reaction efficiency, which is preferable because it shortens the reaction time and reduces the content of impurities.

[0053] The reaction time is not particularly limited, but may be carried out for about 1 hour to 4 hours, preferably 1 hour to 3 hours, after the addition of phosgene is completed.

[0054] Preferably, after the reaction is completed, a step of reducing the temperature inside the reactor to 70°C to 80°C can be further carried out.

[0055] (purification process) Next, the solvent and unreacted phosgene are removed from the reaction mixture. Xylylene diisocyanate The third step involves preparing the composition.

[0056] After the reaction with phosgene is completed, the solvent, unreacted phosgene, etc. remain in the reaction mixture, but these are removed. Xylylene diisocyanate Contains compounds Xylylene diisocyanate A composition is prepared.

[0057] Meanwhile, according to one embodiment of the present invention, the third step may further include a purification step after removing the solvent and unreacted phosgene from the reaction mixture.

[0058] The method for removing and purifying the solvent and phosgene is not particularly limited, and methods commonly used in the art can be applied. For example, unreacted phosgene and hydrogen chloride gas remaining in the reaction mixture can be removed by nitrogen bubbling, and the solvent can be removed by distillation.

[0059] The purification step can be carried out by fractional distillation under reduced pressure and thin-film distillation. In the case of fractional distillation, the plant process can be carried out using a tray distillation column or a packing distillation column. The number of theoretical plates in the distillation column is 2 or more, preferably 5 or more, and preferably 50 or less, or 40 or less.

[0060] Produced by the above-mentioned salt formation reaction, phosgene reaction and purification process Xylylene diisocyanate The composition contains 1% or less of low-boiling compounds relative to the total content of the composition. Here, the low-boiling compounds include isocyanomethylbenzaldehyde and isocyanomethylbenznitrile. The content range of the low-boiling compounds is the GC area (%) measured by gas chromatography (GC), and the specific measurement method will be explained in more detail in the experimental examples described below.

[0061] If the low boiling point compound is contained in an amount exceeding 1%, additional impurities may be generated during the subsequent synthesis of polyisocyanate, inhibiting the activity of the catalyst and affecting the reaction rate. This may affect the quality of the product. However, if the content is adjusted to the appropriate range as described above, Xylylene diisocyanate Use of the composition makes it possible to produce a high-purity polyisocyanate without such problems, and such a polyisocyanate compound can significantly reduce the defect rate when applied to optical articles and improve reproducibility.

[0062] The content of the low boiling point compound is preferably Xylylene diisocyanateThe content of the low-boiling point compound may be 0.7% or less, 0.5% or less, or 0.3% or less relative to the total content of the composition. The lower limit of the content of the low-boiling point compound is 0% or more, preferably 0.0001% or more, 0.0001% to 0.7%, or 0.001 to 0.5%, and the content range is suitable for achieving the above-mentioned effects.

[0063] The isocyanomethylbenzaldehyde (IMBAl) may be contained in an amount of 0.0001 to 0.15%, preferably 0.001 to 0.15%, or 0.0003 to 0.11%, relative to the total content of the composition.

[0064] The isocyanomethylbenznitrile (IMBN) may be contained in an amount of 0.0001 to 0.1%, preferably 0.0003 to 0.1%, or 0.0008 to 0.06%, relative to the total content of the composition.

[0065] According to one embodiment of the present invention, the low-boiling point compound may further include chloromethyl benzyl isocyanate (CMBI), in which case the chloromethyl benzyl isocyanate may be contained in an amount of 0.01 to 0.2%, preferably 0.05 to 0.15%, based on the total content of the composition.

[0066] <Polymerizable composition> According to one embodiment of the invention, Xylylene diisocyanate composition; and A polymerizable composition is provided that includes one or more of i) a multifunctional thiol-based compound and ii) a multifunctional episulfide-based compound.

[0067] The polymerizable composition may contain the isocyanate composition, the polyfunctional thiol compound, and the polyfunctional episulfide compound in a mixed state or in a separated state. That is, in the polymerizable composition, the isocyanate composition and the polyfunctional thiol compound or the polyfunctional episulfide compound may be blended in contact with each other or separated so as not to contact each other.

[0068] The polyfunctional thiol compound may be a compound containing two or more thiol (Thio, —SH) groups in the molecule, and may have an aliphatic, alicyclic, or aromatic skeleton.

[0069] The polyfunctional episulfide compound may be a compound containing two or more episulfides, i.e., thioepoxy groups, in the molecule, and may have an aliphatic, alicyclic, or aromatic skeleton.

[0070] According to one example, the polyfunctional thiol compound is 4,8-bis(mercaptomethyl)-3,6,9-trithiaundecane-1,11-dithiol, 4,7-bis(mercaptomethyl)-3,6,9-trithiaundecane-1,11-dithiol, 5,7-bis(mercaptomethyl)-3,6,9-trithiaundecane-1,11-dithiol, bis(2-mercaptoethyl)sulfide, 4-mercaptomethyl-3,6-dithiaoctane-1,8-dithiol, 2,3-bis(2-mercaptoethylthio)propane-1-thiol, 2,2-bis( ... 2-(2-mercaptomethyl)propane-1,3-dithiol, 2-(2-mercaptoethylthio)propane-1,3-dithiol, 2-(2,3-bis(2-mercaptoethylthio)propylthio)ethanethiol, bis(2,3-dimercaptopropanyl) sulfide, bis(2,3-dimercaptopropanyl) disulfide, 1,2-bis(2-(2-mercaptoethylthio)-3-mercaptopropylthio)ethane, bis(2-(2-mercaptoethylthio)-3-mercaptopropyl)disulfide, 2-(2-mercaptoethylthio)-2-mercapto 2-(2-mercaptoethylthio)-3-mercapto-3-[3-mercapto-2-(2-mercaptoethylthio)-propylthio]propylthio-propane-1-thiol, 2-(2-mercaptoethylthio)-3-mercapto-3-[3-mercapto-2-(2-mercaptoethylthio)-propylthio]propylthio-propane-1-thiol, 2-(2-mercaptoethylthio)-3-(2-(2-[3-mercapto-2-(2-mercaptoethylthio)-propylthio]ethylthio)ethylthio)-propane-1-thiol, (4R,11S)-4,11-bis(mercaptomethyl)-3, 6,9,12-tetrathiatetradecane-1,14-dithiol, (S)-3-((R-2,3-dimercaptopropyl)thio)propane-1,2-dithiol, 4,14-bis(mercaptomethyl)-3,6,9,12,15-pentathiaheptadecane-1,17-dithiol, (S)-3-((R-3-mercapto-2-((2-mercaptoethyl)thio)propyl)thio)propyl)thio)-2-((2-mercaptoethyl)thio)propane-1-thiol, 3,3'-dithiobis(propane-1,2-dithiol), (7R,11S)-7,11-bis(mercaptomethyl)-3,6,9,12,15-pentathiaheptadecane-1,17-dithiol, (7R,12S)-7,12-bis(mercaptomethyl)-3,6,9,10,13,16-hexathiaoctadecane-1,18-dithiol, 2-(2-mercaptoethylthio)-3-[4-(1-{4-[3-mercapto-2-(2-mercaptoethylthio)-propoxy]-phenyl}-1-methylethyl)-phenoxy]-propane-1-thiol, 2,2-bis-(3-mercapto-propionyloxymethyl)-butyl ester, pentaerythritol tetrakis(3-mercaptopropionate), pentaerythritol tetrakis(2-mercaptoethylthio) The mercaptomethylthioester may include one or more selected from the group consisting of bis(mercaptomethylthio)-1,3-dithiane, 2-(2,2-bis(mercaptomethylthio)ethyl)-1,3-dithiane, bispentaerythritol-ether-hexakis(3-mercaptopropionate), trimethylolpropane tris(2-mercaptopropionate), trimethylolpropane tris(3-mercaptopropionate), glycerol trimercaptopropionate, 1,1,3,3-tetrakis(mercaptomethylthio)propane, 1,1,2,2-tetrakis(mercaptomethylthio)ethane, 4,6-bis(mercaptomethylthio)-1,3-dithiane, 2-(2,2-bis(mercaptomethylthio)ethyl)-1,3-dithiane, and 2,5-bismercaptomethyl-1,4-dithiane.

[0071] According to one example, the polyfunctional episulfide-based compound is bis(β-epithiopropylthio)methane, 1,2-bis(β-epithiopropylthio)ethane, 1,3-bis(β-epithiopropylthio)propane, 1,2-bis(β-epithiopropylthio)propane, 1-(β-epithiopropylthio)-2-(β-epithiopropylthiomethyl)propane, 1,4-bis(β-epithiopropylthio)butane, 1,3-bis(β-epithiopropylthio)butane, 1-(β-epithiopropylthio)-3-(β-epithiopropylthiomethyl)butane, 1,5-bis(β-epithiopropylthio)pentane, 1-(β-epithiopropylthio)-4-(β-epithiopropylthiomethyl)pentane, 1,6-bis(β-epithiopropylthio)hexane, 1-(β-epithiopropylthio)-5-(β-epithiopropylthiomethyl)hexane, 1-(β-epithiopropylthio)-2-[(2-β-epithiopropylthioethyl)thio]ethane, 1-(β-epithiopropylthio)-2-[[2-(2-β-epithiopropylthioethyl)thioethyl]thio]ethane, tetrakis(β-epithiopropyl thiomethyl)methane, 1,1,1-tris(β-epithiopropylthiomethyl)propane, 1,5-bis(β-epithiopropylthio)-2-(β-epithiopropylthiomethyl)-3-thiapentane, 1,5-bis(β-epithiopropylthio)-2,4-bis(β-epithiopropylthiomethyl)-3-thiapentane, 1-(β-epithiopropylthio)-2,2-bis(β-epithiopropylthiomethyl)-4-thiahexane, 1,5,6-tris(β-epithiopropylthio)-4-(β-epithiopropylthiomethyl)-3-thiahexane, 1 ,8-bis(β-epithiopropylthio)-4-(β-epithiopropylthiomethyl)-3,6-dithiaoctane, 1,8-bis(β-epithiopropylthio)-4,5-bis(β-epithiopropylthiomethyl)-3,6-dithiaoctane, 1,8-bis(β-epithiopropylthio)-4,4-bis(β-epithiopropylthiomethyl)-3,6-dithiaoctane, 1,8-bis(β-epithiopropylthio)-2,4,5-tris(β-epithiopropylthiomethyl)-3,6-dithiaoctane, 1,8-bis(β-epithiopropylthio)-2,5-Bis(β-epithiopropylthiomethyl)-3,6-dithiaoctane, 1,9-bis(β-epithiopropylthio)-5-(β-epithiopropylthiomethyl)-5-[(2-β-epithiopropylthioethyl)thiomethyl]-3,7-dithianonane, 1,10-bis(β-epithiopropylthio)-5,6-bis[(2-β-epithiopropylthioethyl)thio]-3,6,9-trithiadecane, 1,11-bis(β-epithiopropylthio)-4,8-bis(β-epithiopropylthiomethyl)-3,6,9-trithiaune Decane, 1,11-bis(β-epithiopropylthio)-5,7-bis(β-epithiopropylthiomethyl)-3,6,9-trithiaundecane, 1,11-bis(β-epithiopropylthio)-5,7-[(2-β-epithiopropylthioethyl)thiomethyl]-3,6,9-trithiaundecane, 1,11-bis(β-epithiopropylthio)-4,7-bis(β-epithiopropylthiomethyl)-3,6,9-trithiaundecane, 1,3-bis(β-epithiopropylthio)cyclohexane, 1,4-bis(β-epithiopropylthio) 1,3-bis(β-epithiopropylthiomethyl)cyclohexane, 1,4-bis(β-epithiopropylthiomethyl)cyclohexane, bis[4-(β-epithiopropylthio)cyclohexyl]methane, 2,2-bis[4-(β-epithiopropylthio)cyclohexyl]propane, bis[4-(β-epithiopropylthio)cyclohexyl]sulfide, 2,5-bis(β-epithiopropylthiomethyl)-1,4-dithiane, 2,5-bis(β-epithiopropylthiomethyl)-1,4-dithiane, 2,5-bis(β-epithiopropylthioethylthiomethyl)-1 ,4-dithiane, 1,3-bis(β-epithiopropylthio)benzene, 1,4-bis(β-epithiopropylthio)benzene, 1,3-bis(β-epithiopropylthiomethyl)benzene, 1,4-bis(β-epithiopropylthiomethyl)benzene, bis[4-(β-epithiopropylthio)phenyl]methane, 2,2-bis[4-(β-epithiopropylthio)phenyl]propane, bis[4-(β-epithiopropylthio)phenyl]sulfide, bis[4-(β-epithiopropylthio)phenyl]sulfone, and 4,4'-bis(β-epithiopropylthio)biphenyl.

[0072] In the polymerizable composition, the molar ratio of (thio groups + episulfide groups) to isocyanate groups may be about 0.5 to about 1.5, or about 0.8 to about 1.2, or about 0.9 to about 1.1, but the present invention is not necessarily limited thereto.

[0073] The polymerizable composition may further contain appropriate amounts of additives such as a mold release agent, a heat stabilizer, an ultraviolet stabilizer, a dye, a urethane reaction catalyst, and the like.

[0074] The release agent is a type of surfactant component, and examples thereof include fluorine-based nonionic surfactants containing a perfluoroalkyl group; silicone-based nonionic surfactants containing a dimethylpolysiloxane group; and quaternary ammonium salts such as trimethylcetylammonium salt, trimethylstearyl, dimethylethylcetylammonium salt, triethyldodecylammonium salt, trioctylmethylammonium salt, and diethylcyclohexadodecylammonium salt.

[0075] The heat stabilizer may be, for example, a metal fatty acid salt, a phosphorus-based compound, a lead-based compound, an organotin-based compound, etc. These may be used alone or in combination of two or more.

[0076] The ultraviolet stabilizer may be, for example, a benzophenone-based, benzotriazole-based, salicylate-based, cyanoacrylate-based, or oxanilide-based compound.

[0077] Examples of the dye include fluorescent whitening agents, fluorescent pigments, and inorganic pigments.

[0078] The urethane reaction catalyst may be, for example, a dialkyltin halide compound such as dibutyltin dichloride or dimethyltin dichloride; a dialkyltin dicarboxylate compound such as dimethyltin diacetate, dibutyltin dioctanoate or dibutyltin dilaurate; a dialkyltin dialkoxide compound such as dibutyltin dibutoxide or dioctyltin dibutoxide; a dialkyltin dithioalkoxide compound such as dibutyltin di(thiobutoxide); a dialkyltin oxide compound such as di(2-ethylhexyl)tin oxide, dioctyltin oxide or bis(butoxydibutyltin)oxide; or a dialkyltin sulfide compound, which may be used alone or in combination of two or more.

[0079] <Optical articles> According to one embodiment of the invention, there is also provided an optical article comprising a polythiourethane polymer produced from the polymerizable composition.

[0080] More preferably, the optical article may be an optical lens, such as a spectacle lens, a camera lens, a plastic lens, or a prism.

[0081] <Method for producing polyisocyanate composition> According to another embodiment of the invention, Xylylene diisocyanate A method for producing a polyisocyanate composition is provided by applying the method for producing the composition.

[0082] Specifically, a method for producing a polyisocyanate composition according to one embodiment of the invention includes the steps of: The first step is to react an amine compound with hydrogen chloride in a solvent at 20°C to 90°C and atmospheric pressure to obtain an amine salt compound; Amine salt compounds are reacted with phosgene to form Xylylene diisocyanate a second step of obtaining a reaction mixture containing the compound; removing the solvent and unreacted phosgene from the reaction mixture; Xylylene diisocyanate A third step of preparing the composition; and The aforementioned Xylylene diisocyanateand a fourth step of polymerizing the composition and the polyhydric alcohol to synthesize a polyisocyanate compound.

[0083] The contents of the first, second and third stages are as described above. Xylylene diisocyanate The methods for preparing the compositions are all equally applicable.

[0084] Thereby, the solvent is one or more selected from the group consisting of chlorobenzene, 1,2-dichlorobenzene, 1,4-dichlorobenzene, 1,2,3-trichlorobenzene and 1,2,4-trichlorobenzene, the purity of the amine compound is 99.0% or more, Xylylene diisocyanate The composition contains 1% or less of low-boiling compounds based on the total content of the composition, wherein the low-boiling compounds include isocyanomethylbenzaldehyde and isocyanomethylbenznitrile.

[0085] Next, Xylylene diisocyanate The fourth step involves mixing the composition with a polyhydric alcohol and polymerizing it to synthesize a polyisocyanate compound.

[0086] The isocyanate compound contained in the composition is of high purity, and the content of low-boiling compounds in the composition is 1% or less, so that the generation of by-products in the polymerization stage is significantly reduced.

[0087] Preferably, the polyhydric alcohol is a compound containing two or more hydroxy groups in one molecule, and specifically, may be a compound having two or more, or three or more, and eight or less, or four or less hydroxy groups in one molecule.

[0088] Specific examples include dihydric alcohols such as ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,4-butanediol, 2-methyl-2,3-butanediol, 1,6-hexanediol, and 1,2-hexanediol; trihydric alcohols such as glycerol, trimethylolethane, and trimethylolpropane (TMP); tetrahydric alcohols such as diglycerin, ditrimethylolpropane, pentaerythritol, and dipentaerythritol; pentahydric alcohols such as L-arabinitol, ribitol, and xylitol; hexahydric alcohols such as D-glucitol, D-mannitol, and galactitol, heptahydric alcohols such as trehalose, octahydric alcohols such as sucrose and maltose, and low-molecular-weight polyols. Among these, diethylene glycol, glycerol, trimethylolethane, trimethylolpropane, and mixtures thereof can be used. More specifically, it is preferable to use a trihydric alcohol such as glycerol, trimethylolpropane, or trimethylolethane alone, or to use a mixture of the trihydric alcohol with other polyhydric alcohols.

[0089] On the other hand, the polymerization reaction is a urethane reaction (or addition polymerization reaction) between an isocyanate compound and a hydroxy group in a polyhydric alcohol.

[0090] Therefore, it is preferable to appropriately determine the amount of polyhydric alcohol used, taking into consideration the urethane reaction with the isocyanate compound, the physical properties (e.g., viscosity) to be achieved in the polyisocyanate produced, and the intended use of the polymer. Specifically, the polyhydric alcohol can be added in an amount such that the molar ratio of hydroxy groups in the polyhydric alcohol per mole of isocyanate groups in the isocyanate compound is 0.05 or more, or 0.15 or more and 1 or less, or 0.8 or less. If the molar ratio of hydroxy groups to isocyanate groups is less than 0.05, exceeding this range, the excess isocyanate groups may reduce the viscosity of the produced polymer, resulting in reduced processability. Furthermore, if the molar ratio of hydroxy groups to isocyanate groups exceeds 1, the excess hydroxy groups may reduce the discoloration prevention effect.

[0091] The polymerization reaction may be carried out under atmospheric pressure or in an inert gas atmosphere such as nitrogen or argon.

[0092] The polymerization reaction is preferably carried out at a temperature range of 40°C or higher, or 60°C or higher and 100°C or lower, or 80°C or lower, since this allows the reaction rate to be easily controlled without the risk of discoloration and also increases the reaction efficiency.

[0093] The polymerization reaction may be carried out without a catalyst or in the presence of a catalyst that typically promotes a urethane reaction, such as a tin-based or amine-based catalyst. When the polymerization reaction is carried out in the presence of a catalyst, the catalyst may be added when adding the polyhydric alcohol to the monomer composition.

[0094] The progress of the polymerization reaction can be predicted by measuring the concentration of isocyanate groups in the polymerization product by the n-dibutylamine method using a potentiometric titrator or by measuring the refractive index. In the present invention, the polymerization reaction is carried out until the concentration of isocyanate groups in the polymerization product reaches the calculated value of the isocyanate groups remaining after the reaction with the polyhydric alcohol.

[0095] As a result of such a polymerization reaction, a polyisocyanate is produced.

[0096] The polyisocyanate thus prepared can be reacted with a polyol to prepare polyurethane, and by using the polyisocyanate of the present invention, precise control of the physical properties of polyurethane products is possible.

[0097] Specifically, the polyisocyanate contains urethane bonds formed by reaction of part or all of the isocyanate groups of the isocyanate compound in the reaction mixture obtained by the above-mentioned phosgenation reaction with the hydroxy groups of the polyhydric alcohol.

[0098] The present invention provides a method for producing a high purity Xylylene diisocyanate The low-boiling-point compounds are included, and particularly, when the content of low-boiling-point compounds is 1% by weight or less, a high-purity polyisocyanate can be produced in high yield, and a product without discoloration or cloudiness can be produced. More preferably, the content of low-boiling-point compounds may be 0.7% or less, 0.5% or less, or 0.3% or less, based on the total content of the composition. The lower limit of the low-boiling-point compounds is 0% or more, and preferably 0.0001% or more, 0.0001% to 0.7%, or 0.001 to 0.5%. The content range of the low-boiling-point compounds is the GC area (%) measured by gas chromatography (GC), and the specific measurement method will be explained in more detail in the experimental examples described below.

[0099] In addition to the polyisocyanate, the product obtained as a result of the polymerization reaction may contain a stabilizer that does not participate in the polymerization reaction and an unreacted diisocyanate.

[0100] Therefore, the method for producing a polyisocyanate composition according to one embodiment of the present invention may optionally further include a step of purifying the resultant product after the polymerization reaction is completed to remove unreacted diisocyanate.

[0101] The purification step may be carried out by a conventional purification method such as distillation or solvent extraction, or in the present invention, may be carried out by a distillation purification method such as thin film distillation, which is superior in terms of the efficiency of removing unreacted polyisocyanate.

[0102] The pressure and temperature during the distillation purification step can be appropriately adjusted depending on the composition of the polyisocyanate composition, the distillation apparatus, etc. In the present invention, the distillation purification step may be carried out under a pressure of 0.001 kPa or more and 1 kPa or less, or 0.5 kPa or less.

[0103] The distillation purification step may be carried out at a temperature of 70° C. or higher, or 90° C. or higher and 200° C. or lower, or 180° C. or lower. If the temperature is lower than 70° C., the efficiency of distillation purification may decrease, and if the temperature exceeds 200° C., the polyisocyanate may be denatured by the high temperature.

[0104] The distillation purification step can reduce the content of unreacted diisocyanate in the polyisocyanate composition, and a lower content is preferred because the stability of the composition increases.

[0105] <Polyisocyanate composition> According to another embodiment of the present invention, there is provided a composition produced by the method for producing a polyisocyanate composition.

[0106] The polyisocyanate composition may further contain a dilution solvent, which allows it to exhibit proper applicability and be easily applied to products.

[0107] Preferably, ethyl acetate can be used as the dilution solvent, and may be included so that the isocyanate group content (NCO%) in the composition is 75 wt % of the solid content. By having an isocyanate group content within this range, the polymer composition can exhibit an appropriate crosslink density and exhibit excellent coating film forming properties when coated.

[0108] On the other hand, in the present invention, NCO % is determined by neutralizing the isocyanate groups with an excess of 2N amine and then back-titrating with 1N hydrochloric acid.

[0109] The content of unreacted diisocyanate remaining in the polyisocyanate composition is 1% by weight or less, 0.5% by weight or less, or 0.3% by weight or less, based on the total weight of the solid content in the polyisocyanate composition. This significantly reduces the content of unreacted diisocyanate compared to conventional compositions, thereby enabling the composition to exhibit superior stability.

[0110] The polyisocyanate composition may further contain additives such as an internal mold release agent, an ultraviolet absorber, a polymerization initiator, a heat stabilizer, a color corrector, a chain extender, a crosslinking agent, a light stabilizer, and a filler, as necessary, and the content thereof can be appropriately determined within a range that does not impair the coloring and discoloration suppression properties of the polymer composition.

[0111] The polyisocyanate composition can be used in a wide range of fields due to its excellent physical properties, and in particular, can be used as a pressure sensitive adhesive or adhesive agent due to the excellent adhesive strength of the polyisocyanate composition.

[0112] The functions and effects of the present invention will be described in more detail below through specific examples of the present invention, but these examples are presented only as examples of the present invention and do not define the scope of the invention.

[0113] [Manufacturing example - Xylylene diisocyanate Preparation of the composition Manufacturing Example 1 Into the reactor, 437 kg of 1,2-dichlorobenzene with a purity of 99.83% and m-XDA (meta- Xylylenediamine 45.5 kg (10.4 wt%) of anhydrous hydrochloric acid was added to the reaction mixture at room temperature (approximately 24°C) and atmospheric pressure (1 atm), and 27 kg of anhydrous hydrochloric acid was added and stirred for 3 hours. After adding the anhydrous hydrochloric acid, the temperature rose and the salt formation reaction began. The reactor was maintained at atmospheric pressure (1 atm) and approximately 80°C for approximately 4 hours, and the salt formation reaction proceeded to obtain an amine salt compound.

[0114] Next, after initially charging and injecting 40 kg of phosgene into the reactant containing the amine salt compound, the temperature was raised to 120°C. Additionally, after slowly charging 300 kg of phosgene into the reactor, the temperature of the reactor was maintained at 120 - 135°C. It took 20 hours from the start of phosgene charging to the end of the reaction. After the solution became transparent, the inside of the reactor was cooled to 80°C and cooled by blowing nitrogen. After the phosgene was removed Xylylene diisocyanate a composition was obtained.

[0115] Production Example 2 The same amount as in Production Example 1 was used for the progress. When injecting phosgene, an eductor nozzle was provided at the injection end. After the salt formation reaction ended, the temperature was raised while injecting phosgene at 80°C until it reached 120°C, and the internal temperature was adjusted while adjusting the flow rate of phosgene. The total reaction time took 15 hours in total.

[0116] Production Example 3 The same amount as in Production Example 2 was used for the progress. When injecting phosgene, an eductor nozzle was provided at the injection end. After the salt formation reaction ended, the temperature was raised, and phosgene was injected at 120°C, and the temperature of the reactor was maintained at 120 - 135°C. The total reaction time took 12 hours in total.

[0117] [Experimental Example 1: Analysis of Production Conditions of Isocyanate Compound] For the composition containing the isocyanate compound produced in the above Production Example Xylylene diisocyanate gas chromatography (GC) analysis was performed, and excluding the solvent, the GC area (%) for m-XDI was shown in Table 1 in terms of the purity of m-XDI.

[0118] <GC Analysis Conditions> The phosgene reaction product was analyzed using GC. The GC used for the analysis was HP-6890, and detection was performed with FID. The column used was DB-17 (30 m * 0.25 mm * 0.5 μm), the carrier gas was nitrogen (1.0 mL / min), the injection volume was 1 μl, and the oven temperature was 80°C → 5°C / min → 160°C (8 min) → 20°C / min → 280°C (18 min). Split ratio: Pulsed Splitless method IMBAl detection method: SIM (monitoring ions: m / z 161, 132) CMBI detection method: SIM (monitoring ions: m / z 181, 146) IMBAl detection method: SIM (monitoring ions: m / z 158, 116) [Table 1]

[0119] As can be seen from Table 1, it was confirmed that the reaction uniformity and reaction efficiency differ depending on the phosgene injection method in the phosgene reaction. In particular, when a phosgene mixing eductor is used as in Preparation Examples 2 and 3, it was confirmed that the phosgene and the amine salt compound are mixed uniformly, shortening the reaction time and increasing the purity of m-XDI.

[0120] [Examples and Comparative Examples - Production of Polyisocyanate Compositions] Example 1 Production of isocyanate compounds A reaction mixture containing an isocyanate compound was prepared according to Preparation Example 3 (m-XDA: 10.4 wt%), and the reaction mixture from which phosgene had been removed was subjected to vacuum distillation to remove the solvent. The product was purified by fractional distillation under reduced pressure and thin-film distillation to obtain a product containing an isocyanate compound. Xylylene diisocyanate A composition was obtained.

[0121] Production of polyisocyanate compositions In a nitrogen atmosphere, the above-prepared isocyanate compound (meta- Xylylene diisocyanate ) Xylylene diisocyanate 300 g of the composition was added. The temperature of the flask was raised to 70°C and then maintained at that temperature while 26.7 g of trimethylolpropane (TMP) as a polyhydric alcohol was added dropwise. Thereafter, the reaction temperature was maintained at 70°C until the isocyanate group concentration in the flask reached the calculated value of 33%.

[0122] After the reaction was completed, the resulting reaction product was purified using a thin film evaporator (TFE) to separate unreacted XDI, and then diluted with ethyl acetate to a solid content of 75% by weight to obtain a polyisocyanate composition.

[0123] Example 2 A polyisocyanate composition was obtained in the same manner as in Example 1, except that the amount of m-XDA was changed to 8 wt %.

[0124] Example 3 A polyisocyanate composition was obtained in the same manner as in Example 1, except that the amount of m-XDA was changed to 5 wt %.

[0125] Example 4 An isocyanate compound and a polyisocyanate composition were obtained in the same manner as in Example 1, except that m-XDA having a purity of 99.83% was purified to 99.97% and used.

[0126] Example 5 A polyisocyanate composition was obtained in the same manner as in Example 4, except that the amount of m-XDA was changed to 8 wt %.

[0127] Example 6 A polyisocyanate composition was obtained in the same manner as in Example 4, except that the amount of m-XDA was changed to 5 wt %.

[0128] Comparative Example 1 (Direct Phosgenation Reaction) After filling the flask with 362 ml of 1,2-dichlorobenzene and 42.7 ml of phosgene, the reactor was cooled to -10 to -15°C, and 31.5 ml (8 vol%) of m-XDA was slowly added. After the addition of the amine compound was completed, the reactor was heated to 130°C and maintained at 125 to 135°C until the reaction solution became transparent, allowing the direct phosgenation reaction to proceed. After the reaction solution became transparent, nitrogen was introduced into the reactor and the temperature was reduced to 80°C. The solvent was then removed by vacuum distillation, and the product was purified by fractional distillation under reduced pressure to obtain a composition containing an isocyanate compound and a polyisocyanate composition.

[0129] Comparative Example 2 (Adjusting the Purity of the Reactant) A polyisocyanate composition was obtained in the same manner as in Example 1, except that m-XDA with a purity of 98.0% was used.

[0130] Comparative Example 3 (Solvent Adjustment) A polyisocyanate composition was obtained in the same manner as in Example 1, except that n-amyl acetate was used as the solvent.

[0131] Comparative Example 4 (Adjustment of Process Conditions for Salt Formation Reaction - Pressure) In Example 1, during the salt formation reaction, the pressure was 0.5 to 1.02 kgf / cm at room temperature. 2 A polyisocyanate composition was obtained in the same manner as above, except that the above-mentioned step was changed to the above.

[0132] Comparative Example 5 (Adjustment of Process Conditions for Salt Formation Reaction - Temperature) In Example 1, the reactor temperature was heated to about 120°C during the salt formation reaction. As a result, the amount of XDA.HCl evaporated increased, and a large amount of XDA.HCl salt precipitated in the reactor condenser and lines, making it impossible to obtain a reaction product. As a result, an isocyanate composition could not be obtained.

[0133] Comparative Example 6 (Adjustment of Process Conditions for Salt Formation Reaction - Temperature) In Example 1, a polyisocyanate composition was obtained in the same manner except that the temperature of the reactor was cooled to about 15 ± 1 °C during the salt formation reaction and the reaction was allowed to proceed.

[0134] [Experimental Example 2: Evaluation of Isocyanate Compounds] Gas chromatography (GC) analysis was performed on the reaction mixtures containing the isocyanate compounds prepared in the above Examples and Comparative Examples, and the results are shown in Table 2 in terms of GC area (%).

[0135] <GC Analysis Conditions> The GC used for the analysis was HP-6890, and detection was carried out with FID. The column used was DB-17 (30 m * 0.25 mm * 0.5 μm), the carrier gas was nitrogen (1.0 mL / min), the injection volume was 1 μl, and the oven temperature was 80 °C → 5 °C / min → 160 °C (8 min) → 20 °C / min → 280 °C (18 min). <Content of Unreacted XDA after Salt Formation (%)> After the completion of the salt formation reaction, samples were taken, and the content of the remaining XDA was measured in terms of GC area (%).

[0136] [Experimental Example 3: Analysis of Polyisocyanate Composition] The polyisocyanate compositions prepared in the above Examples and Comparative Examples were measured for chromaticity, NCO content, remaining XDI content, and turbidity evaluation respectively by the methods described below, and the results are shown in Table 2.

[0137] The chromaticity of the prepared polyisocyanate composition sample was evaluated by the APHA method at 25 °C.

[0138] [Experimental Example 4: Evaluation of Optical Articles] 20.8 g of the reaction mixture containing the isocyanate compound prepared in the above Examples and Comparative Examples, 0.04 g of Zelec UN (Stepan), and 0.04 g of Biosorb 583 (Sakai Chemical Industry Co., Ltd.) were stirred in a flask at room temperature for approximately 20 minutes. Next, 0.002 g of dibutyltin chloride was added and stirred for 10 minutes. 19.2 g of 2,3-bis(2-sulfanyl ethyl sulfanyl)propane-1-thiol was added to the mixture, which was then degassed at 5 mbar and stirred for 1 hour to prepare a mixed solution.

[0139] This mixture was filtered through a 1 μm PTFE filter and then poured into a mold consisting of a glass mold and tape. The mold was placed in an oven, and the temperature was gradually increased from 10°C to 120°C, allowing the polymerization reaction to proceed for 20 hours. After polymerization was complete, the mold was removed from the oven and demolded to obtain a plastic lens. The resulting plastic lens was annealed at 120°C for 6 hours to produce the final optical lens sample.

[0140] The degree of cloudiness (transparency) of the manufactured optical lenses was evaluated by the naked eye under various light source conditions according to the following evaluation criteria. The results are shown in Table 2.

[0141] <Evaluation criteria> C (Clear): Transparent under fluorescent and zirconium lamps SH (Slightly lamp Haze): Transparent under fluorescent lamps, but some turbidity is observed under zirconium lamps LH (Lamp Haze): Transparent under fluorescent lamps, but turbidity is observed under zirconium lamps VH (Visual Haze): Turbidity is observed under fluorescent lamps and zirconium lamps. YI: Yellowing is observed on the lens

[0142] [Table 2]

[0143] As can be seen from Table 2, in the examples, high purity ethylene glycol stearate was obtained by a simple manufacturing process in which the purity of the reaction composition was adjusted and the content range of specific low boiling point compounds in the by-products was also adjusted. Xylylene diisocyanate The compound could be prepared in high yield.

[0144] In addition, by adjusting the reaction conditions for the amine compound salt formation within an appropriate range, the process efficiency of the subsequent phosgene reaction can be increased, resulting in high-purity Xylylene diisocyanate The optical lens using this material achieved superior transparency compared to the comparative example. Xylylene diisocyanate It was confirmed that the color value measured by the APHA method was low even after the production of the polyisocyanate composition.

[0145] In the case of the Comparative Examples, it was confirmed that the amount of impurities generated increased due to different process conditions, and the particle size became non-uniform after the salt formation reaction, which inhibited the phosgene reaction, and as a result, the qualities such as transparency and color, which are taken into consideration when applying to products, were lower than those of the Examples.

Claims

1. xylene diisocyanate compounds; and low-boiling compounds including isocyanomethylbenzaldehyde and isocyanomethylbenznitrile; The low-boiling point compound is contained in an amount of 1% or less of the total content of the composition. Xylene diisocyanate composition.

2. The low-boiling point compound is contained in an amount of 0.0001 to 0.7% of the total content of the composition. The xylene diisocyanate composition of claim 1.

3. The isocyanomethylbenzaldehyde is contained in an amount of 0.0001 to 0.15% based on the total content of the composition. The xylene diisocyanate composition of claim 1.

4. The isocyanomethylbenznitrile is contained in an amount of 0.0001 to 0.1% based on the total content of the composition. The xylene diisocyanate composition of claim 1.

5. The low-boiling compound further includes chloromethyl benzyl isocyanate. The xylene diisocyanate composition of claim 1.

6. The chloromethyl benzyl isocyanate is contained in an amount of 0.01 to 0.2% based on the total content of the composition. The xylene diisocyanate composition according to claim 5.

7. A first step of reacting an amine compound with hydrogen chloride in a solvent at 20°C to 90°C and atmospheric pressure to obtain an amine salt compound; a second step of reacting the amine salt compound with phosgene to obtain a reaction mixture comprising a xylene isocyanate compound; and a third step of removing the solvent and unreacted phosgene from the reaction mixture to produce a xylylene diisocyanate composition; the solvent is at least one selected from the group consisting of chlorobenzene, 1,2-dichlorobenzene, 1,4-dichlorobenzene, 1,2,3-trichlorobenzene, and 1,2,4-trichlorobenzene; The purity of the amine compound is 99.0% or more, The xylene diisocyanate composition contains 1% or less of low-boiling compounds based on the total content of the composition, and the low-boiling compounds include isocyanomethylbenzaldehyde and isocyanomethylbenznitrile. Method for producing a xylylene diisocyanate composition.

8. The low-boiling point compound is contained in an amount of 0.0001 to 0.7% of the total content of the composition. A method for producing the xylylene diisocyanate composition according to claim 7.

9. The low-boiling compound further includes chloromethyl benzyl isocyanate. A method for producing the xylylene diisocyanate composition according to claim 7.

10. The amine compound is at least one selected from the group consisting of m-xylylenediamine, p-xylylenediamine, o-xylylenediamine, and chlorides thereof. A method for producing the xylylene diisocyanate composition according to claim 7.

11. The amine compound is contained in an amount of 1 to 20% by weight based on the total content of the solvent. A method for producing the xylylene diisocyanate composition according to claim 7.

12. The solvent is 1,2-dichlorobenzene. A method for producing the xylylene diisocyanate composition according to claim 7.

13. The second stage is carried out at 110°C to 160°C. A method for producing the xylylene diisocyanate composition according to claim 7.

14. The second step is carried out by heating the amine compound in a solvent to a temperature of 110°C to 140°C, and then adding a phosgene compound. A method for producing the xylylene diisocyanate composition according to claim 7.

15. The second step is carried out by injecting phosgene into a reactor containing an amine salt compound through a mixing eductor. A method for producing the xylylene diisocyanate composition according to claim 7.

16. The third step further comprises a purification step after removing the solvent and unreacted phosgene from the reaction mixture. A method for producing the xylylene diisocyanate composition according to claim 7.

17. A first step of reacting an amine compound with hydrogen chloride in a solvent at 20°C to 90°C and atmospheric pressure to obtain an amine salt compound; a second step of reacting the amine salt compound with phosgene to obtain a reaction mixture comprising a xylene diisocyanate compound; a third step of removing the solvent and unreacted phosgene from the reaction mixture to produce a xylylene diisocyanate composition; and a fourth step of polymerizing the xylene diisocyanate composition and a polyhydric alcohol to synthesize a polyisocyanate compound; the solvent is at least one selected from the group consisting of chlorobenzene, 1,2-dichlorobenzene, 1,4-dichlorobenzene, 1,2,3-trichlorobenzene, and 1,2,4-trichlorobenzene; The purity of the amine compound is 99.0% or more, The xylene diisocyanate composition contains 1% or less of low-boiling compounds based on the total content of the composition, and the low-boiling compounds include isocyanomethylbenzaldehyde and isocyanomethylbenznitrile. A method for producing a polyisocyanate composition.

18. The low-boiling point compound is contained in an amount of 0.0001 to 0.7% of the total content of the composition. A method for producing the polyisocyanate composition according to claim 17.

19. The low-boiling compound further includes chloromethyl benzyl isocyanate. A method for producing the polyisocyanate composition according to claim 17.

20. The polyhydric alcohol is a trihydric alcohol or a mixture of the trihydric alcohol with other polyhydric alcohols. A method for producing the polyisocyanate composition according to claim 17.

21. The polyhydric alcohol includes diethylene glycol, glycerol, trimethylolethane, trimethylolpropane, or a mixture thereof. A method for producing the polyisocyanate composition according to claim 17.

22. The second step is carried out in an inert gas atmosphere at a temperature ranging from 40°C to 100°C. A method for producing the polyisocyanate composition according to claim 17.

23. The third step further comprises a purification step after removing the solvent and unreacted phosgene from the reaction mixture. A method for producing the polyisocyanate composition according to claim 17.

24. The xylylene diisocyanate composition according to any one of claims 1 to 6; and i) a multifunctional thiol-based compound and ii) a multifunctional episulfide-based compound, Polymerizable composition.

25. 25. An optical article comprising a polythiourethane polymer made from the polymerizable composition of claim 24.

26. 26. The optical article of claim 25, wherein the optical article is an optical lens.

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